Water-based ink for ink-jet recording

ABSTRACT

A water-based ink for ink-jet recording includes: a solid solution of a quinacridone pigment including C.I. Pigment Red 202 and C.I. Pigment Violet 19; an azo pigment including C.I. Pigment Red 146; and water. A mass ratio (Q:A) of a content amount (Q) of the solid solution of the quinacridone pigment to a content amount (A) of the azo pigment in an entire amount of the water-based ink is in a range of 9:1 to 2:8.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims priority from Japanese Patent ApplicationNo. 2020-080218 filed on Apr. 30, 2020, the disclosure of which isincorporated herein by reference in its entirety.

BACKGROUND Field of the Invention

The present invention relates to a water-based ink for ink-jetrecording.

Description of the Related Art

Conventionally, it is known to use a solid solution containing two ormore kinds of pigments in a water-based ink for ink-jet recording, tothereby improve the characteristic of the water-based ink for ink-jetrecording (see Japanese Patent Application Laid-open No. 2018-150515corresponding to United States Patent Application Publication No.US2018/0258302).

On the other hand, in the ink-jet recording, the color development(coloring) of a color in the red range is important in view of thevisibility. Although it is conceivable that the color development of thecolor in the red range can be achieved by improving a red ink, it ispreferred to achieve the color development of the color in the red rangeby improving a magenta ink which is included in the three primary colorswhich are yellow, magenta and cyan.

However, in a case that any attempt is made so as to reproduce a targetcolor by singly using a solid solution containing not less than twokinds of pigments, there arises such a problem that the colorreproduction range is narrow and/or that the chromaticness at a part inwhich the colors are mixed is lowered, etc. Thus, there is a high demandfor achieving a wide color reproduction range from magenta (hue angle:approximately −40 degrees) to red (hue angle: approximately 40 degrees),and there is also a demand for improvements in the chromaticness ofmagenta and in the recording density.

In view of the above situation, an object of the present teaching is toprovide a water-based ink for ink-jet recording which is capable ofachieving the wide color reproduction range from magenta to red, andwhich has satisfactory chromaticness of magenta and satisfactoryrecording density (optical density), as well.

SUMMARY

According to the present teaching, there is provided a water-based inkfor ink-jet recording including:

a solid solution of a quinacridone pigment including C.I. Pigment Red202 and C.I. Pigment Violet 19;

an azo pigment including C.I. Pigment Red 146; and

water, wherein a mass ratio (Q:A) of a content amount (Q) of the solidsolution of the quinacridone pigment to a content amount (A) of the azopigment in an entire amount of the water-based ink is in a range of 9:1to 2:8.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph explaining the synergistic effect of the presentteaching, and is a view indicating colors (chromaticities) of evaluationsamples, respectively, in the L*a*b* color system chromaticity diagramindicating a* and b* on a plane, each of the evaluation samples beingprepared in (a) evaluation of hue angle of Examples 1 to 17 andComparative Examples 1 to 6.

FIG. 2 is a schematic perspective view depicting the configuration of anexample of an ink jet recording apparatus related to the presentteaching.

DESCRIPTION OF THE EMBODIMENT

In the present teaching, the chromaticness (C*) is calculated, forexample, based on a* and b* which are based on the L*a*b* color system(CIE 1976 (L*a*b*) color system) normalized or standardized byCommission Internationale d'Eclairage (CIE) in 1976 (see, JIS Z 8729).

C*={(a* ²)+(b* ²)}^(1/2)

In the present teaching, the term “hue angle” represents, for example,an angle in the L*a*b* color system chromaticity diagram (a*-b* plane)indicating a* and b* on a plane, and is defined as follows:

In a*≥0, b*≥0 (first quadrant), the hue angle=tan⁻¹(b*/a*);

In a*≤0, b*≥0 (second quadrant), the hue angle=180 degrees+tan⁻¹(b*/a*);

In a*≤0, b*≤0 (third quadrant), the hue angle=180 degrees+tan⁻¹(b*/a*);and

In a*≥0, b*≤0 (fourth quadrant), the hue angle=360 degrees+tan⁻¹(b*/a*).

A water-based ink for ink-jet recording (hereinafter also referred to asa “water-based ink” or an “ink”, in some cases) related to the presentteaching will be explained. The water-based ink related to the presentteaching includes a quinacridone pigment, an azo pigment and water.

The quinacridone pigment contains a solid solution containing C.I.Pigment Red 202 (hereinafter referred to as “PR202” in some cases) andC.I. Pigment Violet 19 (hereinafter referred to as “PV19” in somecases). In the present teaching, the term “solid solution” means apigment which is present as a mixed crystal of two or more kinds ofpigment molecules (in a mixed crystallized state), and is different frombeing as simply mixing two or more kinds of pigments to each other. Thesolid solution may be a quinacridone pigment which contains at leastPR202 and PV19; it is allowable that the solid solution contains aquinacridone pigment which is different from PR202 and PV19 (hereinafterreferred to as “another pigment”), or that the solid solution does notcontain the another pigment. In a case that the solid solution containsthe another pigment, the content ratio of the another pigment in theentire amount of the solid solution is, for example, smaller than thecontent amount of the solid solution in the entire amount of thewater-based ink, and smaller than the content amount of the C.I. PigmentRed 146 in the entire amount of the water-based ink. The content ratioof the another pigment in the entire amount of the solid solution is,for example, less than 0.3% by mass, not more than 0.1% by mass, or 0%by mass. Further, it is allowable to use, as the solid solutioncontaining PR202 and PV19, a commercially available product; or it isallowable to produce the solid solution containing PR202 and PV19 by apublicly known producing method.

A content amount (Q) of the quinacridone pigment in the entire amount ofthe water-based ink is, for example, in a range of 0.5% by mass to 10%by mass, in a range of 1% by mass to 9% by mass, or in a range of 1% bymass to 7% by mass.

The quinacridone pigment included in the water-based ink may be only thesolid solution containing PR202 and PV19. Alternatively, the water-basedink may further contain a quinacridone pigment which is different fromthe solid solution containing the PR202 and PV19, in addition to thesolid solution containing PR202 and PV19. In the water-based ink, themass ratio of the solid solution containing PR202 and PV19 in the entireamount of the quinacridone pigment is, for example, not less than 50% bymass, not less than 70% by mass, or 100% by mass.

The azo pigment contains C.I. Pigment Red 146 (hereinafter referred toas “PR146” in some cases). C.I. Pigment Red 146 is a non-solid solutionpigment which does not construct a solid solution with another pigment,and which is dispersed in the water-based ink.

A content amount (A) of the azo pigment in the entire amount of thewater-based ink is, for example, in a range of 0.5% by mass to 10% bymass, in a range of 0.5% by mass to 8% by mass, or in a range of 0.5% bymass to 6% by mass.

The azo pigment included in the water-based ink may be only PR146.Alternatively, the water-based ink may further contain an azo pigmentwhich is different from PR146, in addition to PR146. In the water-basedink, the mass ratio of PR146 in the entire amount of the azo pigment is,for example, not less than 50% by mass, not less than 70% by mass, or100% by mass.

A mass ratio (Q:A) of the content amount (Q) of the quinacridone pigmentto the content amount (A) of the azo pigment in the entire amount of thewater-based ink is in a range of Q:A=9:1 to 2:8. The mass ratio (Q:A) ofthe content amount (Q) of the quinacridone pigment to the content amount(A) of the azo pigment in the entire amount of the water-based ink maybe, for example, in a range of Q:A=7:3 to 4:6.

Since the water-based ink uses the solid solution which contains PR202and PV19 in combination with PR146 and the mass ratio (Q:A) of thecontent amount (Q) of the quinacridone pigment to the content amount (A)of the azo pigment in the entire amount of the water-based ink is madeto be in the range of Q:A=9:1 to 2:8, the water-based ink is capable ofachieving the wide color reproduction range from magenta to red, and hassatisfactory chromaticness of magenta and satisfactory recordingdensity, as well.

For example, the color (chromaticness) of an image formed by using thewater-based ink related to the present teaching is plotted at a positionat which the chromaticness is high (a position separate and away fromthe origin), in the region from magenta to red (wherein the hue angle isin a range of approximately −40 degrees to approximately 40 degrees) inthe a*-b* plane. This indicates that the water-based ink related to thepresent teaching is capable of achieving a wide color reproduction rangefrom magenta to red. This effect of the water-based ink related to thepresent teaching (the above-described wide color reproduction range)exceeds an arithmetic mean intermediate level of the solid solutioncontaining PR202 and PV19, and PR146. As depicted in FIG. 1, thearithmetic mean intermediate level is on a straight line connecting aplot of Comparative Example 1 (to be described later on) singly usingthe solid solution containing PR202 and PV19, and a plot of ComparativeExample 2 (to be described later on) singly using PR146. In contrast, inExamples 1 to 17 (to be described later on) each using the solidsolution containing PR202 and PV19 in combination with PR146, the a* andb* exceed the above-described straight line, and exhibit the synergisticeffect. Here, in the water-based ink (Examples 1 to 17) of the presentteaching, “a* and b* exceeded the straight line” means that the straightline is located between the plot of the water-based ink of the presentteaching and the origin in the a*-b* plane shown in FIG. 1. Namely, itmeans that the chromaticness of the water-based ink of the presentteaching is higher than the chromaticness of the water-based ink plottedon the straight line having the same hue angle as the water-based ink ofthe present teaching. It is presumed that the water-based ink of thepresent teaching achieves the above-described synergistic effectsbecause intrinsic absorption peaks of PV19, PR202 and PR146appropriately overlap. This mechanism, however, is merely a presumption,and the present teaching is not limited to or restricted by thispresumed mechanism. Note that a* and b* as described above are based onthe L*a*b* color system (CIE 1976 (L*a*b*) color system) normalized orstandardized by Commission Internationale d'Eclairage (CIE) in 1976(see, JIS Z 8729).

A total (Q+A) of the content amount (Q) of the quinacridone pigment andthe content amount (A) of the azo pigment in the entire amount of thewater-based ink is, for example, in a range of 5% by mass to 9% by mass,in a range of 5% by mass to 8% by mass, in a range of 6% by mass to 8%by mass or in a range of 6% by mass to 9% by mass.

In a case that the total (Q+A) is made to be the range of 5% by mass to9% by mass, it is possible to obtain a water-based ink which is furtherexcellent in the balance among the hue angle, the chromaticness ofmagenta and the recording density.

In a case that the mass ratio (Q:A) is made to be in the range ofQ:A=7:3 to 4:6, and that the total (Q+A) is made to be in the range of5% by mass to 8% by mass, it is possible to obtain a water-based inkwhich is further excellent the balance among the hue angle, thechromaticness of magenta and the recording density.

In a case that the mass ratio (Q:A) is made to be in the range ofQ:A=7:3 to 4:6, and that the total (Q+A) is made to be the range of 6%by mass to 8% by mass, it is possible to obtain a water-based ink whichis particularly excellent in the recording density, in addition to beingfurther excellent in the balance among the hue angle, the chromaticnessof magenta and the recording density.

In a case that the mass ratio (Q:A) is made to be in the range ofQ:A=7:3 to 5:5, and that the total (Q+A) is made to be the range of 6%by mass to 9% by mass, it is possible to obtain a water-based ink whichis particularly excellent in the recording density, in addition to beingfurther excellent in the balance among the hue angle, the chromaticnessof magenta and the recording density.

It is allowable that the water-based ink further contains a pigment anda dye, etc., which are different from the quinacridone pigment and theazo pigment, in addition to the quinacridone pigment and the azopigment, or that the water-based ink does not further contains a pigmentand a dye, etc., which are different from the quinacridone pigment andthe azo pigment.

The pigment usable for the water-based ink is exemplified, including thequinacridone pigment and the azo pigment, by: C. I. Pigment Reds 2, 3,5, 6, 7, 12, 15, 16, 48, 48:1, 53:1, 57, 57:1, 112, 122, 123, 139, 144,146, 149, 150, 166, 168, 175, 176, 177, 178, 184, 185, 190, 202, 221,222, 224 and 238; C. I. Pigment Violets 19 and 196; C.I. Pigment Yellows1, 2, 3, 12, 13, 14, 15, 16, 17, 55, 73, 74, 75, 78, 83, 93, 94, 95, 97,98, 114, 128, 129, 138, 150, 151, 154, 180, 185 and 194; C. I. PigmentOranges 31 and 43; etc. Among the above-described pigments, thequinacridone pigment and the azo pigments are particularly preferred.

The water-based ink may be a water-based ink in which the pigment isdispersed in water by a dispersant. As the dispersant, it is allowableto use, for example, a general polymeric dispersant (resin fordispersing pigment, or pigment-dispersing resin), etc. The pigment maybe a self-dispersible pigment. The self-dispersible pigment isdispersible in water without using any dispersant, for example, owing tothe fact that at least one of the hydrophilic group and the salt thereofincluding, for example, a carbonyl group, a hydroxyl group, a carboxylicacid group, a sulfonic acid group, and a phosphate group is introducedinto the surfaces of the pigment particles by the chemical bond directlyor with any group intervening therebetween.

The water is preferably ion-exchanged water or pure water (purifiedwater). The content amount of the water in the entire amount of thewater-based ink may be, for example, in a range of 10% by mass to 90% bymass or in a range of 20% by mass to 80% by mass. The content amount ofthe water in the entire amount of the water-based ink may be, forexample, a balance of the other components.

The water-based ink may further contain a surfactant. The surfactant isexemplified, for example, by an acetylene glycol-based surfactant, etc.

It is allowable to use, for example, any commercially available productas the acetylene glycol-based surfactant. The commercially availableproduct is exemplified, for example, by: “OLFIN (trade name) E1004”,“OLFIN (trade name) E1008” and “OLFIN (trade name) E1010” which areproduced by NISSHIN CHEMICAL CO., LTD.; “SURFYNOL (trade name) 440”,“SURFYNOL (trade name) 465” and “SURFYNOL (trade name) 485” which areproduced by AIR PRODUCTS AND CHEMICALS, Inc.; “ACETYLENOL (trade name)E40” and “ACETYLENOL (trade name) E100” produced by KAWAKEN FINECHEMICALS CO., LTD.; and the like.

It is allowable that the water-based ink further contains anothersurfactant which is different from the acetylene glycol-basedsurfactant, in addition to or instead of the acetylene glycol-basedsurfactant, or that the water-based ink does not further contain theanother surfactant. The another surfactant is exemplified, for example,by: nonionic surfactants of “EMULGEN (trade name)” series, “RHEODOL(trade name)” series, “EMASOL (trade name)” series, “EXCEL (trade name)”series, “EMANON (trade name)” series, “AMIET (trade name)” series,“AMINON (trade name)” series, etc., produced by KAO CORPORATION;nonionic surfactants of “SORBON (trade name)” series produced by TOHOCHEMICAL INDUSTRY CO., LTD.; nonionic surfactants of “DOBANOX (tradename)” series, “LEOCOL (trade name)” series, “LEOX (trade name)” series,“LAOL, LEOCOL (trade name)” series, “LIONOL (trade name)” series,“CADENAX (trade name)” series, “LIONON (trade name)” series, “LEOFAT(trade name)” series, etc., produced by LION CORPORATION; anionicsurfactants of “EMAL (trade name)” series, “LATEMUL (trade name)”series, “VENOL (trade name)” series, “NEOPELEX (trade name)” series, NSSOAP, KS SOAP, OS SOAP, and “PELEX (trade name)” series, etc., producedby KAO CORPORATION; anionic surfactants of “LIPOLAN (trade name)”series, “LIPON (trade name)” series, “SUNNOL (trade name)” series,“LIPOTAC (trade name)” series, “TE, ENAGICOL (trade name)” series,“LIPAL (trade name)” series, and “LOTAT (trade name)” series, etc.,produced by LION CORPORATION; cationic surfactants “KACHIOGEN (tradename) ES-OW” and “KACHIOGEN (trade name) ES-L” produced by DAI-ICHIKOGYO SEIYAKU CO., LTD., etc. It is allowable that only one kind of theanother surfactant as described above is used singly, or two or morekinds of the another surfactant are used in combination.

The content ratio of the surfactant is, for example, not less than 4parts by mass, in a range of 11 parts by mass to 20 parts by mass, or ina range of 12 parts by mass to 17 parts by mass, to the total, of thecontent amount of the quinacridone pigment and the content amount of theazo pigment, which is 100 parts by mass. In a case that the contentratio of the surfactant is in the above-described range, ink dropletsare appropriately wet and spread on the surface of the recording medium,and thus an image quality is expected to be improved.

The water-based ink may further contain a water-soluble organic solvent.The water-soluble organic solvent is exemplified, for example, by ahumectant which prevents the ink from drying at an end of a nozzle in anink-jet head, a penetrant which adjusts the drying velocity on arecording medium, etc.

The humectant is not particularly limited, and is exemplified, forexample, by: lower alcohols such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol,and tert-butyl alcohol; amides such as dimethylformamide anddimethylacetamide; ketones such as acetone; ketoalcohols (ketonealcohols) such as diacetone alcohol; ethers such as tetrahydrofuran anddioxane; polyethers such as polyalkylene glycol; polyvalent alcoholssuch as alkylene glycol, glycerol, trimethylolpropane,trimethylolethane; 2-pyrrolidone; N-methyl-2-pyrrolidone;1,3-dimethyl-2-imidazolidinone; and the like. The polyalkylene glycol isexemplified, for example, by polyethylene glycol, polypropylene glycol,etc. The alkylene glycol is exemplified, for example, by ethyleneglycol, propylene glycol, butylene glycol, diethylene glycol,triethylene glycol, dipropylene glycol, tripropylene glycol,thiodiglycol, hexylene glycol, etc. It is allowable that only one kindof the humectant as described above is used singly, or two or more kindsof the humectant are used in combination. Among the above-describedhumectants, it is preferable to use polyvalent alcohols such as alkyleneglycol, glycerol, etc.

The content amount of the humectant in the entire amount of thewater-based ink is, for example, in a range of 0% by mass to 95% bymass, in a range of 5% by mass to 80% by mass, or in a range of 5% bymass to 50% by mass.

The penetrant is exemplified, for example, by glycol ether. The glycolether is exemplified, for example, by ethylene glycol methyl ether,ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, diethyleneglycol methyl ether, diethylene glycol ethyl ether, diethyleneglycol-n-propyl ether, diethylene glycol-n-butyl ether, diethyleneglycol-n-hexyl ether, triethylene glycol methyl ether, trimethyleneglycol ethyl ether, triethylene glycol-n-propyl ether, triethyleneglycol-n-butyl ether, propylene glycol methyl ether, propylene glycolethyl ether, propylene glycol-n-propyl ether, propylene glycol-n-butylether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether,dipropylene glycol-n-propyl ether, dipropylene glycol-n-butyl ether,tripropylene glycol methyl ether, tripropylene glycol ethyl ether,tripropylene glycol-n-propyl ether, tripropylene glycol-n-butyl ether,etc. One kind of the penetrant may be used singly, or two or more kindsof the penetrant may be used in combination.

The content amount of the penetrant in the entire amount of thewater-based ink is, for example, in a range of 0% by mass to 20% bymass, in a range of 0% by mass to 15% by mass, or in a range of 1% bymass to 6% by mass.

The water-based ink may further contain a conventionally known additive,as necessary. The additive includes, for example, pH-adjusting agents,viscosity-adjusting agents, surface tension-adjusting agents,fungicides, fixing agents for glossy paper, etc. The viscosity-adjustingagents include, for example, polyvinyl alcohol, cellulose, water-solubleresin, etc.

The water-based ink can be prepared, for example, such that thequinacridone pigment, the azo pigment, the water, and optionally otheradditive component(s) as necessary are mixed uniformly or homogeneouslyby any conventionally known method, and undissolved matters are removedby a filter or the like.

The hue angle of the water-based ink may be, for example, in a range of−5 degrees to 11 degrees, or in a range of −2 degrees to 7 degrees. Theabove-described range of the hue angle is in the vicinity of the centerin the range from magenta to red (wherein the hue angle is in a range ofapproximately −40 degrees to approximately 40 degrees). By making thehue angle of the water-based ink to be in the vicinity of the center inthe range from magenta to red, it is possible to easily reproduce acolor in the range from magenta to red in a case that printing isperformed together with another color (for example, yellow). Note thatthe hue angle of the water-based ink may be measured, for example, bypreparing an evaluation sample by using the water-based ink, and bymeasuring the hue angle of the evaluation sample, as will be explainedin Examples (to be described later on).

Next, an ink-jet recording apparatus related to the present teachingwill be explained.

The ink-jet recording apparatus related to the present teaching ischaracterized by including: an ink storing section and an inkdischarging mechanism, wherein an ink stored in the ink storing sectionis discharged by the ink discharging mechanism, and wherein thewater-based ink for ink-jet recording related to the present teaching isstored in the ink storing section.

FIG. 2 depicts an example of the configuration of the ink-jet recordingapparatus related to the present teaching. As depicted in FIG. 2, anink-jet recording apparatus 1 includes, as main constitutive components,four ink cartridges 2, an ink jetting (discharging) mechanism (ink-jethead) 3, a head unit 4, a carriage 5, a driving unit 6, a platen roller7, and a purge device 8.

Each of the four ink cartridges 2 contains one color ink of four colorwater-based inks which are water-based yellow, magenta, cyan, and blackinks. For example, the water-based magenta ink is the water-based inkfor ink-jet recording related to the present teaching. In this exemplaryembodiment, a set of the four ink cartridges 2 are depicted. However, inplace of this four-ink cartridge set, it is also allowable to use anintegrated type ink cartridge in which the interior thereof is compartedso that a water-based yellow ink accommodating section, a water-basedmagenta ink accommodating section, a water-based cyan ink accommodatingsection, and a water-based black ink accommodating section are formed.As a main body of the ink cartridge, for example, any conventionallyknown main body of an ink cartridge may be used.

The ink-jet head 3 disposed on the head unit 4 performs recording on arecording medium P (for example, recording paper P or recording papersheet P). The four ink cartridges 2 and the head unit 4 are provided orarranged on the carriage 5. The driving unit 6 reciprocates the carriage5 in a linear direction. As the driving unit 6, it is possible to use,for example, a conventionally known driving unit (see, for example,Japanese Patent Application Laid-open No. 2008-246821 corresponding toUnited States Patent Application Publication No. US2008/0241398 A1). Theplaten roller 7 extends in a reciprocating direction of the carriage 5and is arranged to face the ink-jet head 3.

The purge device 8 sucks or draws unsatisfactory ink (poor ink) whichcontains air bubbles, etc., accumulated or trapped in the inside of theink-jet head 3. As the purge device 8, it is possible to use, forexample, a conventionally known purge device (for example, see JapanesePatent Application Laid-open No. 2008-246821 corresponding to UnitedStates Patent Application Publication No. US2008/0241398 A1).

A wiper member 20 is provided on the purge device 8 at a position on theside of the platen roller 7 such that the wiper member 20 is adjacent tothe purge device 8. The wiper member 20 is formed to have a spatulashape, and wipes a nozzle-formed surface of the ink-jet head 3accompanying with the movement (reciprocating movement) of the carriage5. In FIG. 2, a cap 18 is provided to cover a plurality of nozzles ofthe ink-jet head 3 which is returned to a reset position upon completionof recording, so as to prevent the water-based inks from drying.

In the ink-jet recording apparatus 1 of the present embodiment, the fourink cartridges 2 are provided, together with the head unit 4, on onecarriage 5. However, the present teaching is not limited to this. In theink-jet recording apparatus 1, the respective four ink cartridges 2 maybe provided on a carriage which is different (separate) from thecarriage on which the head unit 4 is provided. Alternatively, therespective four ink cartridges 2 may be arranged and fixed inside theink-jet recording apparatus 1, rather than being provided on thecarriage 5. In such aspects, for example, the four ink cartridges 2 areconnected to the head unit 4 provided on the carriage 5 with tubes,etc., and the water-based inks are supplied from the four ink cartridges2 via the tubes, respectively, to the head unit 4. Further, in theseaspects, it is allowable to use four ink bottles having a bottle shape,instead of using the four ink cartridges 2. In such a case, each of theink bottles is preferably provided with an inlet port via which the inkis poured from the outside to the inside of each of the ink bottles.

Ink-jet recoding, with the use of the ink-jet recording apparatus 1, isperformed, for example, as follows. At first, the recording paper P issupplied from a paper feed cassette (not depicted in the drawings)provided at a side portion or a lower portion of the ink-jet recordingapparatus 1. The recording paper P is introduced into a space betweenthe ink-jet head 3 and the platen roller 7. A predetermined recording isperformed on the introduced recording paper P with the water-basedink(s) jetted or discharged from the ink-jet head 3. The recording paperP after having the recording performed thereon is discharged from theink-jet recording apparatus 1. According to the present teaching, it ispossible to obtain a printed matter in which the wide color reproductionrange from magenta to red is achievable, and which has satisfactorychromaticness of magenta and satisfactory recording density, as well. Apaper feeding mechanism and a paper discharging mechanism for therecording medium P are omitted from the illustration in FIG. 2.

The apparatus depicted in FIG. 2 adopts the serial type ink-jet head.However, the present teaching is not limited to or restricted by this.The ink-jet recording apparatus may be an apparatus which adopts a linetype ink-jet head.

Next, an ink-jet recording method of the present teaching is an ink-jetrecording method of discharging a water-based ink onto a recordingmedium in the ink-jet system so as to thereby perform recording on therecording medium, characterized by using of the water-based ink forink-jet recording of the present teaching, as the water-based ink. Therecording includes printing text (character, letter), printing image orpicture, and printing, etc.

EXAMPLES

Next, Examples of the present teaching will be explained together withComparative Examples. Note that the present teaching is not limited toand restricted by Examples and Comparative Examples described below.

<Preparation of Aqueous Pigment Dispersions A to D>

Pure water (purified water) was added to 20% by mass of a pigment (asolid solution of PR202 and PV19) and 7% by mass of sodiumhydroxide-neutralized product of styrene-acrylic acid copolymer (acidvalue: 175 mgKOH/g, molecular weight: 10000) so that the entire amountthereof was 100% by mass, followed by being agitated and mixed, and thusa mixture was obtained. The obtained mixture was placed in a wet sandmill charged with zirconia beads of which diameter was 0.3 mm, and wassubjected to a dispersing process for 6 (six) hours. Afterwards, thezirconia beads were removed by a separator, and the mixture wasfiltrated through a cellulose acetate filter (pore size 3.0 μm). Thus,aqueous pigment dispersion (water pigment dispersion) A indicated inTABLE 1 and TABLE 2 was obtained. Note that the styrene-acrylic acidcopolymer is a water-soluble polymer which is generally used as adispersant for pigment (pigment dispersant). Further, aqueous pigmentdispersions B to D indicated in TABLE 1 and TABLE 2 were obtained in asimilar manner regarding the aqueous pigment dispersion A except forappropriately changing the kind of pigment, the component ratio and theduration time of dispersing process.

Examples 1 to 17 and Comparative Examples 1 to 6

Components, which were included in Ink Composition (TABLE 1 or TABLE 2)and which were different from the aqueous pigment dispersions A to D,were mixed uniformly or homogeneously; and thus an ink solvent wasobtained. Subsequently, the obtained ink solvent was added to each ofthe aqueous pigment dispersions A to D, followed by being mixeduniformly, and thus a mixture was obtained. After that, the obtainedmixture was filtrated through a cellulose acetate membrane filter (poresize 3.00 μm) produced by TOYO ROSHI KAISHA, LTD., and thus awater-based ink for ink jet recording of each of Examples 1 to 17indicated in TABLE 1 and Comparative Examples 1 to 6 indicated in TABLE2 was obtained.

With respect to the water-based inks of Examples 1 to 17 and ComparativeExamples 1 to 6, respectively, (a) Evaluation of Hue Angle, (b)Evaluation of Chromaticness of Magenta, and (c) Evaluation of RecordingDensity were performed by the following methods.

(a) Evaluation of Hue Angle

The water-based ink of each of Examples 1 to 17 and Comparative Examples1 to 6 was coated on or applied to a recording medium (“Hammermill Fore(trade name) Multi-Purpose Paper” produced by INTERNATIONAL PAPERCOMPANY) so that a coating (application) amount per unit area was madeto be approximately 0.90 mg/cm²; thus, an evaluation sample wasprepared. The hue angles at 5 (five) locations in the evaluation samplewere measured by using a spectrophotometric colorimetry meter“SpectroEye” produced by X-RITE INC., the average value of the hueangles at the five locations was obtained, and the hue angle wasevaluated based on the following evaluation criterion.

<Criterion for Evaluation of Hue Angle>

A: The hue angle was in a range of not less than −2 degrees to not morethan 7 degrees.

B: The hue angle was in a range of not less than −5 degrees to less than−2 degree, or the hue angle exceeded 7 degrees and was not more than 11degrees.

C: The hue angle was less than −5 degrees or exceeded 11 degrees.

(b) Evaluation of Chromaticness of Magenta

The values of chromaticness (C*) at 5 (five) locations in the evaluationsample in (a) the evaluation of hue angle as descried above weremeasured by using the spectrophotometric colorimetry meter “SpectroEye”,the average value of the values of chromaticness (C*) at the fivelocations was obtained, and the chromaticness of magenta was evaluatedbased on the following evaluation criterion.

<Criterion for Evaluation of Chromaticness of Magenta>

A: The chromaticness (C*) was not less than 70.

B: The chromaticness (C*) was in a range of not less than 66 to lessthan 70.

C: The chromaticness (C*) was less than 66.

(c) Evaluation of Recording Density

The optical densities (OD values) at 5 (five) locations in theevaluation sample in (a) the evaluation of hue angle as descried abovewere measured with the spectrophotometric colorimetry meter, SpectroEye(light source: D₅₀; field: 2 degrees; ANSI-T); the average value of theOD values measured at the five locations were obtained, and therecording density was evaluated based on the following evaluationcriterion.

<Criterion for Evaluation of Recording Density>

AA: The optical density (OD value) was not less than 1.30.

A: The optical density (OD value) was in a range of not less than 1.20to less than 1.30.

B: The optical density (OD value) was in a range of not less than 1.12to less than 1.20.

C: The optical density (OD value) was less than 1.12.

The ink composition and the results of evaluations of each of thewater-based inks of Examples 1 to 17 and Comparative Examples 1 to 6 areindicated in TABLE 1 and TABLE 2.

Table 1 (Following)—Legend

*1: Aqueous dispersion of the solid solution of PR202 and PV19; numeralin the parenthesis indicates pigment solid concentration (% by mass) inthe aqueous dispersion.

*2: Aqueous dispersion of PR146; numeral in the parenthesis indicatespigment solid concentration (% by mass) in the aqueous dispersion.

*3: Nonionic surfactant (acetylene glycol-based surfactant); produced byNISSHIN CHEMICAL CO., LTD.; numeral in the table indicates the effectiveingredient amount.

The unit in the ink composition in TABLE 1: % by mass

TABLE 1 EXAMPLES 1 2 3 4 5 6 7 8 9 Ink composition Quinacridone Aqueouspigment 45  40  35  42  49  56  63  30  25  (% by mass) pigment (Q)dispersion A (*1) (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10) Azo pigment Aqueous pigment 5 10  15  18  21  24  27  20  25  (A)dispersion B (*2) (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10) Humectant 86% Glycerol 8 8 8 8 8 8 7 8 8 Penetrant Triethylene glycol- 22 2 2 2 2 2 2 2 n-butyl ether Surfactant OLFIN (trade name) 1 1 1 1 1 11 1 1 E1010 (*3) Water balance balance balance balance balance balancebalance balance balance Q:A 9:1 8:2 7:3 7:3 7:3 7:3 7:3 6:4 5:5 Q + A 55 5 6 7 8 9 5 5 (a) Hue Angle B B A A A A A A A (b) Chromaticness ofMagenta B B A A A A A A A (c) Recording Density A A A AA AA AA AA A AEXAMPLES 10 11 12 13 14 15 16 17 Ink composition Quinacridone Aqueouspigment 20  24  28  32  36  15  10  45  (% by mass) pigment (Q)dispersion A (*1) (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10)  Azopigment Aqueous pigment 30  36  42  48  54  35  40  45  (A) dispersion B(*2) (10)  (10)  (10)  (10)  (10)  (10)  (10)  (10)  Humectant 86%Glycerol 8 8 8 8 7 8 8 7 Penetrant Triethylene glycol- 2 2 2 2 2 2 2 2n-butyl ether Surfactant OLFIN (trade name) 1 1 1 1 1 1 1 1 E1010 (*3)Water balance balance balance balance balance balance balance balanceQ:A 4:6 4:6 4:6 4:6 4:6 3:7 2:8 5:5 Q + A 5 6 7 8 9 5 5 9 (a) Hue AngleA A A A B A A A (b) Chromaticness of Magenta A A A A A B B A (c)Recording Density A AA AA AA AA A A AA

TABLE 2 COMPARATIVE EXAMPLES 1 2 3 4 5 6 Ink composition QuinacridoneAqueous pigment 50  — — — — 5 (% by mass) pigment (Q) dispersion A (*1)(10)  (10)  Aqueous pigment — — 15  —  10.5 — dispersion C (*4) (10) (10)  Aqueous pigment — — — 15    4.5 — dispersion D (*5) (10)  (10) Azo pigment Aqueous pigment — 50  35  35  35  45  (A) dispersion B (*2)(10)  (10)  (10)  (10)  (10)  Humectant 86% Glycerol 8 8 8 8 8 8Penetrant Triethylene glycol- 2 2 2 2 2 2 n-butyl ether Surfactant OLFIN(trade name) 1 1 1 1 1 1 E1010 (*3) Water balance balance balancebalance balance balance Q:A 10:0 0:10 3:7 3:7 3:7 1:9 Q + A 5 5 5 5 5 5(a) Hue Angle C B A C A A (b) Chromaticness of Magenta B C C B C C (c)Recording Density B C B B C B TABLE 2 - LEGEND (*1): Aqueous dispersionof the solid solution of PR202 and PV19; numeral in the parenthesisindicates pigment solid concentration (% by mass) in the aqueousdispersion. (*4): Aqueous dispersion of PR202; numeral in theparenthesis indicates pigment solid concentration (% by mass) in theaqueous dispersion. (*5): Aqueous dispersion of PV19; numeral in theparenthesis indicates pigment solid concentration (% by mass) in theaqueous dispersion. (*2): Aqueous dispersion of PR146; numeral in theparenthesis indicates pigment solid concentration (% by mass) in theaqueous dispersion. (*3): Nonionic surfactant (acetylene glycol-basedsurfactant); produced by NISSHIN CHEMICAL CO., LTD.; numeral in thetable indicates the effective ingredient amount. The unit in the inkcomposition in TABLE 2: % by mass

As indicated in TABLE 1, in Examples 1 to 17, the evaluation resultswere satisfactory in relation to all of (a) Evaluation of Hue Angle, (b)Evaluation of Chromaticness of Magenta, and (c) Evaluation of RecordingDensity. Since the hue angle and the chromaticness of magenta were bothsatisfactory in Examples 1 to 17, it was confirmed that Examples 1 to 17were each capable of achieving the wide color reproduction range frommagenta to red.

Regarding Examples 3 to 6 and 8 to 13 in each of which Q:A was made tobe in the range of Q:A=7:3 to 4:6 and Q+A was made to be in the range ofQ+A=5% by mass to 8% by mass were further excellent in the balance amongthe hue angle, the chromaticness of magenta and the recording density,as compared with Examples 1, 2, 15 and 16 in each of which Q:A was made9:1, 8:2, 3:7 or 2:8, and as compared with Example 14 in which Q+A wasmade to be Q+A=9% by mass. Further, regarding Examples 4 to 7 and 17 ineach of which Q:A was made to be in the range of Q:A=7:3 to 5:5 and Q+Awas made to be in the range of Q+A=6% by mass to 9% by mass weresimilarly further excellent in the balance among the hue angle, thechromaticness of magenta and the recording density, as compared withExamples 1, 2 and 14 to 16.

Regarding Examples 4 to 6 and 11 to 13 in each of which Q:A was made tobe in the range of Q:A=7:3 to 4:6 and Q+A was made to be in the range ofQ+A=6% by mass to 8% by mass were excellent in the hue angle and thechromaticness of magenta, and further excellent in the recordingdensity, as compared with Examples 1 to 3, 8 to 10 and 14 to 16 in eachof which Q+A was made to be Q+A=5% by mass or 9% by mass. Further,regarding Examples 4 to 7 and 17 in each of which Q:A was made to be inthe range of Q:A=7:3 to 5:5 and Q+A was made to be in the range ofQ+A=6% by mass to 9% by mass were similarly excellent in the hue angleand the chromaticness of magenta and further excellent in the recordingdensity, as compared with Examples 1 to 3, 8 to 10 and 14 to 16.

On the other hand, as indicated in TABLE 2, Comparative Example 1 whichdid not use the azo pigment had a unsatisfactory result in (a)Evaluation of Hue Angle. Further, Comparative Example 2 which did notuse the quinacridone pigment had unsatisfactory results in (b)Evaluation of Chromaticness of Magenta and (c) Evaluation of RecordingDensity. Furthermore, Comparative Example 3 which used the PR202 as thequinacridone pigment, rather than using the solid solution containingPR202 and PV19, had an unsatisfactory result in (b) Evaluation ofChromaticness of Magenta, and Comparative Example 4 which used the PV19as the quinacridone pigment, rather than using the solid solutioncontaining PR202 and PV19 had an unsatisfactory result in (a) Evaluationof Hue Angle. Moreover, Comparative Example 5 which used a non-solidsolution of the PR202 and a non-solid solution of PV19 as thequinacridone pigment, rather than using the solid solution containingPR202 and PV19, had unsatisfactory results (b) Evaluation ofChromaticness of Magenta and (c) Evaluation of Recording Density.Further, Comparative Example 6 in which Q:A was made to be Q+A=1:9 hadan unsatisfactory result in (b) Evaluation of Chromaticness of Magenta.

As described above, the water-based ink related to the present teachingis capable of achieving the wide color reproduction range from magentato red, and has satisfactory chromaticness of magenta and satisfactoryrecording density, as well. The water-based ink related to the presentteaching is widely applicable to a variety of kinds of the ink-jetrecording, for example, as a water-based magenta ink for ink-jetrecording.

What is claimed is:
 1. A water-based ink for ink-jet recordingcomprising: a solid solution of a quinacridone pigment including C.I.Pigment Red 202 and C.I. Pigment Violet 19; an azo pigment includingC.I. Pigment Red 146; and water, wherein a mass ratio (Q:A) of a contentamount (Q) of the solid solution of the quinacridone pigment to acontent amount (A) of the azo pigment in an entire amount of thewater-based ink is in a range of 9:1 to 2:8.
 2. The water-based ink forink-jet recording according to claim 1, wherein a total (Q+A) of thecontent amount (Q) of the solid solution of the quinacridone pigment andthe content amount (A) of the azo pigment in the entire amount of thewater-based ink is in a range of 5% by mass to 9% by mass.
 3. Thewater-based ink for ink-jet recording according to claim 2, wherein themass ratio (Q:A) of the content amount (Q) of the solid solution of thequinacridone pigment to the content amount (A) of the azo pigment in theentire amount of the water-based ink is in a range of 7:3 to 4:6; andthe total (Q+A) of the content amount (Q) of the solid solution of thequinacridone pigment and the content amount (A) of the azo pigment inthe entire amount of the water-based ink is in a range of 5% by mass to8% by mass.
 4. The water-based ink for ink jet recording according toclaim 3, wherein the total (Q+A) of the content amount (Q) of the solidsolution of the quinacridone pigment and the content amount (A) of theazo pigment in the entire amount of the water-based ink is in a range of6% by mass to 8% by mass.
 5. The water-based ink for ink-jet recordingaccording to claim 2, wherein the mass ratio (Q:A) of the content amount(Q) of the solid solution of the quinacridone pigment to the contentamount (A) of the azo pigment in the entire amount of the water-basedink is in a range of 7:3 to 5:5; and the total (Q+A) of the contentamount (Q) of the solid solution of the quinacridone pigment and thecontent amount (A) of the azo pigment in the entire amount of thewater-based ink is in a range of 6% by mass to 9% by mass.
 6. Thewater-based ink for ink-jet recording according to claim 1, furthercomprising a surfactant, wherein a ratio of a content of the surfactantto a total of 100 parts by mass of a content of the solid solution ofthe quinacridone pigment and a content of the azo pigment is not lessthan 4 parts by mass.
 7. The water-based ink for ink jet recordingaccording to claim 6, wherein the ratio of the content of the surfactantto the total of 100 parts by mass of the content of the solid solutionof the quinacridone pigment and the content of the azo pigment is in arange of 11 parts by mass to 20 parts by mass.
 8. The water-based inkfor ink-jet recording according to claim 6, wherein the surfactant is anacetylene-glycol based surfactant.
 9. The water-based ink for ink-jetrecording according to claim 1, wherein a hue angle of the water-basedink is in a range of −5 degrees to 11 degrees.
 10. The water-based inkfor ink-jet recording according to claim 9, wherein the hue angle of thewater-based ink is in a range of −2 degrees to 7 degrees.
 11. Thewater-based ink for ink jet recording according to claim 1, furthercomprising a quinacridone pigment which is different from the solidsolution.